Dear all:

Hubert Wadepohl wrote:
> in a recent paper (Stein, Lenthe, Baerends, Lubitz, J. Phys. Chem. A 2001,
> 105, 416) the effect of spin-orbit coupling and spin polarization on ESR
> parameters was evaluated for certain organometallic radicals.
>
> In particular, several scalar relativistic (SR) calculations were
> performed to evaluate electron-nuclear hyperfine interactions:
> (1) spin-orbit+SR restricted open shell
> (2) SR unrestricted
> (3) SR restricted open shell
>
> Cases (1) and (3) are described in the adf-200 manual and work ok.
> However, when I try case (3) adf-2000 does not calculate hyperfine
> couplings. Is there a way to force it to do so? After all adf-1999 was
> used to get the values listed in the above paper.

Answer:
For case (3) do a SR restricted open shell calculation,
save TAPE21, and use the whole molecule as a fragment
in a SR unrestricted calculation with the keywords:
 scf
  iter 0
 end
This will do the trick.
ADF wil use the fragment density coming from the spin-restricted
calculation as start-up density in the unrestricted calculation.
iter 0 means that only 1 scf-iteration will be performed
with the use of the fragment density (one should
use the same XC-potential in both calculations of course),
such that the alpha-orbital energies remain degenerate
with the beta-orbitals.
Example inputfile TiF3 SR restricted open shell, see below.

Best regards
Erik van Lenthe

------------------------------------------------------
Afdeling Theoretische Chemie, Vrije Universiteit,
De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
Tel. : +31 20 44 47615
secretary: 44 47519
 fax.: 44 47629
 e-mail: vlenthe_at_chem.vu.nl
------------------------------------------------------

Example inputfile TiF3 SR restricted open shell:

$ADFBIN/dirac -n1 < $ADFRESOURCES/Dirac/Ti
rm FILE* logfile

$ADFBIN/dirac -n1 < $ADFRESOURCES/Dirac/F
rm FILE* logfile

mv TAPE12 t12.rel

$ADFBIN/adf -n1 << eor
Create Ti $ADFRESOURCES/ZORA/V/Ti
relativistic scalar zora
Corepotentials t12.rel &
Ti 1
end

end input
eor

mv TAPE21 t21.ti
rm [A-Z]* logfile

$ADFBIN/adf -n1 << eor
Create F $ADFRESOURCES/ZORA/V/F
relativistic scalar zora
Corepotentials t12.rel &
F 2
end

end input
eor

mv TAPE21 t21.f
rm [A-Z]* logfile

$ADFBIN/adf << eor
title TiF3 scalar relativistic restricted

DEFINE
 RTIF = 1.780
 RY = RTIF*SQRT(3)/2
END

atoms
  Ti 0 0 0
  F RTIF 0 0
  F -RTIF/2 RY 0
  F -RTIF/2 -RY 0
end

fragments
  Ti t21.ti
  F t21.f
end

xc
  GGA Becke Perdew
end

relativistic scalar zora
Corepotentials t12.rel &
  Ti 1
  F 2
end

end input
eor

mv TAPE21 t21.TiF3
rm [A-Z]* logfile

$ADFBIN/adf << eor
title TiF3 scalar relativistic open shell restricted

DEFINE
 RTIF = 1.780
 RY = RTIF*SQRT(3)/2
END

esr
end

qtens

atoms
  Ti 0 0 0 f=TiF3
  F RTIF 0 0 f=TiF3
  F -RTIF/2 RY 0 f=TiF3
  F -RTIF/2 -RY 0 f=TiF3
end

fragments
  TiF3 t21.TiF3
end

xc
  GGA Becke Perdew
end

charge 0 1
unrestricted

scf
 iter 0
end

relativistic scalar zora
Corepotentials t12.rel &
  Ti 1
  F 2
end

end input
eor

rm [A-Z]* logfile
Received on 2001-11-05 14:23:37